Solid-State Coordination Chemistry of the Cu/Triazolate/X System (X = F-, Cl-, Br-, I-, OH-, and SO42-)

Hydrothermal reactions of 1,2,4-triazole with the appropriate copper salt have provided eight structurally unique members of the Cu/triazolate/X system, with X = F-, Cl-, Br-, I-, OH-, and SO4(2-). The anionic components X of [Cu3(trz)4(H2O)3]F2 (1) and [Cu6(trz)4Br]Cu4Br4(OH) (4) do not participate in the framework connectivity, acting as isolated charge-compensating counterions. In contrast, the anionic subunits X of [Cu(II)Cu(I)(trz)Cl2] (2), [Cu6(trz)4Br2] (3), [Cu(II)Cu(I)(trz)Br2] (5), [Cu3(trz)I2] (6), [Cu6(II)Cu2(I)(trz)6(SO4)3(OH)2(H2O)] (8), and [Cu4(trz)3]OH.7.5H2O (9.7.5H2O) are intimately involved in the three-dimensional connectivities. The structure of [Cu(II)Cu(I)(trz)2][Cu3(I)I4] (7) is constructed from two independent substructures: a three-dimensional cationic {Cu2(trz)2}n(n+) component and {Cu3I4}n(n-) chains. Curiously, four of the structures are mixed-valence Cu(I)/Cu(II) materials: 2, 5, 7, and 8. The only Cu(II) species is 1, while 3, 4, 6, and 9.7.5H2O exhibit exclusively Cu(I) sites. The magnetic properties of the Cu(II) species 1 and of the mixed-valence materials 5, 7, 8, and the previously reported [Cu3(trz)3OH][Cu2Br4] have been studied. The temperature-dependent magnetic susceptibility of 1 conforms to a simple isotropic model above 13 K, while below this temperature, there is weak ferromagnetic ordering due to spin canting of the antiferromagnetically coupled trimer units. Compounds 5 and 7 exhibit magnetic properties consistent with a one-dimensional chain model. The magnetic data for 8 were fit over the temperature range 2-300 K using the molecular field approximation with J = 204 cm(-1), g = 2.25, and zJ' = -38 cm(-1). The magnetic properties of [Cu3(trz)3OH][Cu2Br4] are similar to those of 8, as anticipated from the presence of similar triangular {Cu3(trz)3(mu3-OH)}(2+) building blocks. The Cu(I) species 3, 4, 6, and 9 as well as the previously reported [Cu(5)(trz)3Cl2] exhibit luminescence thermochromism. The spectra are characterized by broad emissions, long lifetimes, and significant Stokes' shifts, characteristic of phosphorescence.